Stabilization of halogen containing organic materials



Patented Nov. 17, 1942 a STABILIZATION .ORGAN IC MATERIALS or" HALOGENCONTAINING llohannes Nelles, Leverkusen-Schlebusch," and v .Otto Bayer,Leverkusen-I. G. Werlr, Germany;

vested lathe Alien Property Custodian No Drawing. Application September27, 19 39, Sle- H rial 1938 r The present invention reiates to a new'comcomprising chlor ne contain-' I v y 32, page 2035., By the .additionbfs'uchstabilizers' position of matter ing substances. V I

Itis known that many organic halogen contain'ing substances show atendency of splitting oi! partof the halogen in the form of hydrogenhalide, if exposed to an elevated temperature, In many cases suchtendency is to be observed even at normal temperature.flThlsfisftrue,for

instance, in case of chlorinated or brominated low and high molecularaliphatic compounds;

such as, for instance, chlorinated paramnic hydrocarbons, .lchlorinatedrubber, chlorobutadiene polym'erisates, polyvinylchloride, polymeric'vinyi' chloroacetate and'mixed polymerisates containing suchingredients. Finally, there may be men tioned chlorinated acids andesters, 'as'for instance, chlorinated fats, oils and train oils. 1

No. 296,808. In Germanyfebruary 1 io chums. (auto-r);- y

' propyleneeimines are h s known from 'Ber. d.

Deutsch.Chem. ,Ges." voll 31, page 3265 and vol.

the substances having the tendency to split off As 'a matter'of fact,the practical use of such halogen containing compound s can be considerably handicapped or even completely destroyed by such undesirableproperties. It-is the object of this'invention'to' do away with these'disad vantages and to develop a new type ofstabilizers fol suchcompounds which combinewith the hydrogen halide, which might be splitoil, at the.

very moment of its formation and convert "the same into a harmlesssubstance, so that free hydrogen halide cannot be found presence of suchcompounds. y

'We havefound that the tendency of splitting of! hydrogenhalide ofsuch'compounds can be avoided by incorporating therewith:certainstabillzing agents which may be defined 'asNacyl ethylene-iminesor the corresponding'propyleneimines." Our new stabilizers correspond tothe following formulae: i i I can be prepared in various ways, forinstance,

by causing organic acid chlorides to react upon ethylene-lmine orsubstitution products thereof. The corresponding propylene-imines can beprewithin or in the hydrogen halide are stabilized in such a way thateven after avery long heatingto an elevated temperature no free:hydrogen halide can be found}, The new stabilizer shows, a neutral reaction, and, therefore, there is no danger in-;

volved thereby .ofany chemical interaction with the substances to bestabilized. In general, the stabilizing effect of such compounds is suchthat an amount of about 0.5 to about 10 per cent is suthcient forthe'purpose-in question. The

stabilizer must becapable of being .homogenously incorporated within thecompound to be stabilized, at least partly, I 7

Theincorporation of our stabilizers within the haYogen containingsubstances to be stabilized may be eifccted in various ways, forinstance, by mixing the substances with or without dissolving orswellingagentsybyworking the mixture on as is more fully explained above.

the roller and so on. It is also possible, to add the stabilizer beforeorduring the preparation 01' such halogen containing. compounds, 1. e.,dur-, ing the polymerization of halogen containing substances, such as,chlorobutadiene so that they are in this way incorporated within thefinal. prod ucts.. I

material, provided, however, that the stabilizer is compatible with thecompoundto be stabilized In case high molecular halogen containingsubstances are em-, ployed,.such as chlorinated natural or' syntheticrubber. or polyvinylchioride.care should be taken,

that the stabilizer has a boiling point above about 180C. in order toprevent the same from evappared by acylating propylene-imines which are,

described in Berichte der Deutschen Chemisorating from the saidmaterials. The new compositions may contain various other ingredientssuch as filling materials. pigments, softeners and the like.

The present invention is illustrated by the following examples:

Example 1 N-benzenesulfonyl-ethylene-imine (prepared by causingbenzenesulfonyl chloride to react with chen Gesellschaft, vol. 21, page2677. N acyl ethylene-mime) and heated to C. After It is to beunderstood'that the term acylf' heating for 30 hours at this temperatureIII, page2933). 1 I a I. Similar results are obtained by replacing the jthe solution-"does not show an acid reaction. The same solution; withoutthe addition of the stabilizer under the same conditions splits onhydrogen chloride even after heating it for minutes.

Instead of N-benzenesulionyl-ethylene-imine there canbeemployedilbstearoyl-ethyiene-imine (prepared from stearoyl' chloride andethyleneimine) or N-benzoylethylene-imine (Berichte 2. The compositionof mattera s claimed in claim. 6 wherein the N-benzoylethylene-imine ispresent in an amount between about 0.5 and 10% of the amount oi thehalogen containing substance. V

3. The composition of matter comprising a member of the groupconsistlngot N-acyl ethylene-imines and N-acyl propylene-imines and anorganic substance containing organically derDeutschen ChemischenGesellschai't. vol. 28;

chlorinated rubber by polyvinylchloride, fpoly- 'meric 2-chlorobutadieneor Q-bromObutadiene or by chlorinated butadiene-'l. 3-polymerisates. Ilmmple zh H Chlorinated parainn (ehlorinecchtent; is mixed with 2 percent by weightot an acylated bound halogen and showing the tendency ofsplitting of! halogen in form of hydrogen halide the N-acyl-imine beingpresent in an amount sufllcient to. neutralize any halogenhalide split01! irom the halogen containing substance.

" 4. The composition of matter comprising a member oi the groupconsisting of N-acyl ethyl'ene-imines and 'N-acyl-propylene imines andethylene-imine which has been preparedin thev usual way by causingchlorides of acids obtained by the oxidation drparamninuxturejor ca toC10) with ethylene-Amine. Contrary'to the. chlorin ated pa'raflinitself. this mixture does not split on. any free hydrogen chloride evenafter heat ng the same to roo c; for a'longftime. I Enami) 3.,

1 .Amyicm'onde is mixed with! cent by weight of N-benzoylethylene imineand heated'to 150 C; After heatingthe mixture Ior 'lO' days a strip ofCongo-paper, dipped into the liquid,

i -w he Weed 1 A'tter chlorinated polyvinylchlcride' is treat e with 5%N-benzoylethylene-imine. The mass thus obtained is essentiallymoreystable at-l C. th an it "is without thestabiliz ing addition.

'."E u l mple 5" I l 1A 30% solution of chlorinated-rubber in xylene ismixedwith 5% (calculated on the chlorinated rubbery o!N-benzenesu1fonyl-propylene imine (produced from cyclopropylene-imineandbenaenesulfonic' chloride) and heated to '100. C.

After heatingthe solution for btlhours, it does not show anacidreaction; The same solution without-addition oi the stabilizer;however, un-

. der the same conditions splits 0!! hydrogen flan organic substancecontaining organically bound halogen and showing the tendency ofsplitting ofi halogen in form of hydrogen halide. the ior'mer beingpresent therein in an amount between about 0.5 and -10% of theamount ofthe halogen containing substance. f I I 5. The composition of mattercomprising N-benzenesulionyl-ethylene-imine an or ganic substancecontaining organically bound,

halogen and showing the tendency of splitting oil halogen in form ofhydrogen halide the former being present in an amountsufilcient toneutralize any halogenhalide split on from the halogen containingsubstance.

6. The composition 01 matter comprising N-benzoylethylene-iminq and anorganic substancecontaining organically bound halogen and showing thetendencyfot splitting of! halogen in form of hydrogenhalide theiformerbeing present in an amount sufllcient toneutralizeany halogen halidesplit of! from the. halogen containing substance, I A i 7. The.composition of... matter comprising chlorinated rubber and a member ofthe group consisting of N -acyl ethylene-imine's and N acylpropylene-imines the latter being present in an amount sumcient toneutralize any hydrogen chloride split of! from the chlorinated rubber.

8.The composition of matter. comprising 7 chlorinated rubber ands.member oi the group chloride 'even afterbein'g h'eatedior 15 minutes. i

In thesarne way otherchlorinated or brominated materials, such as,for-instance, tats,'oils, train stabilized. v, I @We'cIaim oil,ethyienetetrachloride-and' the like maybe v1. The composition oimatteras claimed in claim 15 wherein the 'N- benzenesuli'orwl-ethyleneimine.is present in an amount between about 1 0.5 and 10% of the amount of thehalogencontainingsubstanca fJ the chlorinated rubber.

consisting of Nacyl-ethylene-imines and N-acylpropylene-imines, thelatter being present there:

in in an amount between about 0.5 and'l0% o! the amountof thechlorinatedrubber,

9. The composition oi. matter comprising chlorinated rubberandN-be'nzoyl ethylene-imine thelatter being present in an amountsuillcient toneutralize any hydrogen chloride. split or! from 10..Thecomposition of matter comprising chlorinated rubber and between about0.5 and about 10% thereof of N-benzoyl ethylene-imine.

JOI-IANNES NELLES. o'rro BAYER. 1

